Production of aromatic nitriles



amaze PRODUCTION OF AROMATIC NITRILES wuufm i. ut. Biahop,lladdonfleid,

Vacuum Oil Company.

tion of New York No Drawing.

Woodburr, and- Richard B.

N. 1., assignora to Socony- Incorporated, a corpora- Application February 20, 1946, Serial No. 649,118

11 ohm (01.260465) I This invention relates to ing aromatic nitriles and is more particularly concerned with a catalytic process -!or producing aromatic nitriles from aromatic hydrocarbons.

Aromatic nitrilesareorganic compounds containing "combined nitrogen. Their :iormula may be represented thus: R-CEN, in which R is an aryl'group. These compounds are very useful since they can be converted readily. to many valuable products such as acids, amines, aldehydes, esters, etc.

As is well known to those familiar with the art, several processes have been proposed for the preparation of aromatic nitriles. In general, however, all of these processes have been disadvana process tor productageous from one or more standpoints, namel the relatively high cost of the reactants employed and/or the toxic nature of some of the reactants and/or ultimate reparation. For example, aromatic hithe number of operations involved in their J triles have been synthesized by reacting alkali cyanides with aromatic sulionates or with aromatic-substituted'alkyl halides; by reacting more complex cyanides such nide, with diazonium halides; by reacting isothiocyanatesv with copper or with zinc dust; and by reacting aryl aldoximes with acyl halides.

We have now found a process for producing aromatic nitriles which is simple and inexpensive, and which employs non-toxic reactants.

We have discovered that aromatic nitriles can be prepared by reacting alkyl aromatic hydrocarbons with ammonia at elevated temperatures, in the presence of catalytic material containing vanadium oxide.

Our'invention is to be distinguished from the conventional processes for the production of hydrogen cyanide wherein carbon compounds, such as carbon monoxide, methane, and benzene, are reacted with ammonia at elevated temperatures in the presence of alumina, nickel, quartz, clays, oxides of thorium and cerium, copper, iron oxide, silver, iron, cobalt, chromium, aluminum phosphate, etc. The process of the present invention isalso to be'distinguished from the processes of the prior art for the production of amines wherein mrdrocarbons are reacted with ammonia at high temperatures, or at lower'temperatures in the presence of nickel.

Accordingly, it is an object of the present invention to provide a process for the production of aromatic nitriles. Another object is to afford a catalytic process for the production of aromatic nitriles. An important object is to provide a procas potassium cuprous cyaess for producing aromatic nitriles which is in;

u when used per so, they generally possess addi- 'terial containing vanadium vention will become apparent to those skilled in the art from the following description.

Broadly stated, our pensive and commercially feasible process for the production of aromatic nitriles, which comprises reacting an alkyl aromatic hydrocarbon'with ammonia, in the gaseous phase and at elevated temperatures, in the presence of catalytic maoxide. Generally speaking, any alkyl aromatic hydrocarbon is suitable as the hydrocarbon reactant in the process of our invention. The alkyl-substituted aromatic hydrocarbons to be used in the process of our invention may be derived from any suitable source as is well known to those familiar with the art. Although any alkyl-substituted aromatichydrocarbon may be employed for our purpose, we prefer to use the methyl-substituted aromatic hydrocarbons, or those in 'which the alkyl substitnent or at least one of the alkyl substituents is'unsaturated, andmore particularly, the thus alkyl-substituted benzenes. Examples are toluene, xylenes, and trimethyl benzenes, and styrene.

-It is to be understood, however, that hydrocarbon matic hydrocarbons, such as methyl-substituted naphthalenes, and fractions containing the same may be employed'in the present process.

The proportions of reactants, i. e., alkyl aromatic hydrocarbon and ammonia, used in our process may be varied over a wide range with little effect on the conversion per pass and ultimate yield. In general, the charge of reactants may contain as little as 2 mol., or as much as 98 mol. of alkyl aromatic hydrocarbons. In practice, however, we use charges containing between about 20 mol. and about 90' mol. or alkyl aromatic hydrocarbon, and ordinarily, we prefer to use charges containing a molar excess of ammonia over the alkyl aromatic hydrocarbon reactant.

We have found that the catalysts to be used to produce the aromatic nitriles, by reacting alkyl aromatic hydrocarbons with ammonia, are those containing a vanadium oxide, such as vanadium monoxide (V0), vanadium trioxide (V203), vanadium dioxide (V02) and vanadium pentoxide (V205) it must be clearly understood that when we speak of vanadium oxide, herein and in the claims, we have reference to the various oxides of vanadium. We have found, however, that vanadium pentoxide is to be preferred as a starting catalytic material. v

While vanadium oxide catalysts are effective tional catalytic activity when used in conjunction with the well known catalyst supports, such as invention provides an inex- Therefore, and in the interest of brevity,

. the catalyst under and the like. We especiall refer to use alumina (A1203) as a catalyst support, and we have found that a'catalyst comprising vanadium pentoxide supported on alumina is particularly useful for our purpose. Without any intent of limiting the scope of the present invention, it is suspected that the enhanced catalytic activity of the supported catalysts is attributable primarily to their relatively large surface area. v

The concentration of vanadium oxide in the S pported catalysts influences the conversion per pass. In general, the conversion per pass increases with increase in the concentration of vanadium oxide. For example, we have found our process vary between about 850 pheric pressure, we have found that the space velocities may be varied considerably and that velocities varying between about one-fourth to about 4 are quite satisfactory for the purposes of the present invention.

In general, the temperatures to be used in F. and up to the decomposition temperature or ammonia (about 1250-1300-F.), and preferably, temperatures varyingbetween about 925 F. and about 1075 F. The preferred temperature to be used in any particular operation will depend upon the nature of hydrocarbon reactant used and upon that a catalyst comprising parts by weight of vanadium pentoxide on 80 parts by weight of alumina is more effective than one comprising 10 parts by weight of vanaduim pentoxide on 90 parts by weight of alumina. It is to be understood, however, that supported catalysts containing larger or smaller amounts of vanadium oxide may be usedin our process.

We have found also that in order to obtain initial'maximum catalytic efliciency, particularly where the catalytic material comprises the higher oxides of vanadium, that the catalysts should be conditioned prior to use in the process; As defined herein, conditioned catalysts are those which have been exposed to ammonia or hydrogen, or both, fora period of time, several minutes to several hours, depending upon the quanat temperatures varying between about 800 F. and about 1300" F. However, if desired, the conditioning treatment may be dispensed with inasmuch as the catalyst becomes conditionedduring the initial stages of our proces when the catalyst comes in contact with the ammonia reactant.

In operation, the catalysts become fouled with carbonaceous material which ultimately aifects their catalytic activity. Accordingly, when the efliciency of the catalyst declines to a point where further operation becomes uneconomical or disadvantageous from a practical standpoint, the catalyst may. be regenerated as is well known in the art, by subjecting the same to a careful oxidation treatment, for example, by passing a stream of air or air diluted with flue gases over appropriate temperature conditions and for a suitable period of time, such as the same period of time as the catlaytic operation. Preferably, the oxidation treatment is followed by a purging treatment, such as passing over the catalyst a stream of purge gas, for example, nitrogen, carbon dioxide, hydrocarbon gases, etc.

The reaction or contact time, i. e., the period of time during which a unit volume of the reactants is in contact with a unit volume of catalyst, may vary between a fraction of a second and several minutes. Thus, the contact time may be as low as 0.01 second and a high as 20 minutes. We prefer to use contact times varying between 0.1 second and one minute, particularly, between 0.3 second and 30 seconds. It must be realized that these figures are at best estimates based on a number of assumptions. For all practical purposes, as in catalytic processes or the type of the present invention, the more reliable data on contact time is best expressed, as is well known in the art, in terms of liquid space velocities, in the present instance, the volume of liquid hydrocarbon reactant per volume of catalyst per hour. For example, at atmosthe type of catalyst employed. Generally speaking, the higher temperatures increase the conversion per pass but they also increase the decomposition of the reactants thereby decreasing the ultimate yields of aromatic nitriles. Accordingly, the criteria for determining the op-- timum temperature to be used in any particular operation will be based on the nature of the hydrocarbon reactant, the type of catalyst, and a consideration of commercial feasibility from the standpoint of striking a practical balance between conversion per pass and losses to decomposition.

The process of the present invention may be carried out at subatmospheric, atmospheric or superatmospheric pressures. Superatmospheric pressures are advantageous in that the unreactcd charge materials condense more readily. Subatmospherlc pressures appear to favor the reactions involved since the reaction products have a larger volume thanthe reactants, and hence, it is evident from the law of Le Chatelier-Braun that the equilibrium favors nitrile formation more at reduced pressures. However, such pressures reduce the throughput of the reactants and present increased diiliculties in recycling unreacted charge materials. Therefore, atmospheric pressure or superatmospheric pressures are preferred.

At the present time. the reaction mechanism involved in the process of the present invention is not fully understood. Fundamentally, the simplest possible method of making aromatic nitriles is to introduce nitrogen directly into the alkyl radical of the alkyl aromatic hydrocarbon molecule, thereby avoiding intermediate steps with their accompanying increased cost. In our process, we have noted that considerable amounts of hydrogen are evolved; hence, it is postulated, without any intent of limiting the scope of the present invention, that the aromatic nitriles are formed in accordance with the following equations, using toluene, xylene and mesitylene as examples:

The present process may be carried out by making use oi any of the well-known techniques for operating catalytic reactions in the vapor phase bers, it will be seen that as effectively. Bywa or illustration, toluene and ammonia may be brought together in suitable proportions andthe mixture vaporized in a preheating zone. The vaporized mixture is then introduced into a reaction zone containing a catalyst of the type defined hereinbefore. The reaction zone may be a chamber of any suitable type useful in contact-catalytic operations; for example, a catalyst bed contained in a shell, or a shell through which the catalyst flows concurrently, or countercurrently, with the reactants, The vapors of the reactants are maintained in contact with the catalyst at a predetermined elevated temperature and for a predetermined period of time, both as set forth hereinbefore, and the resulting reaction mixture is passed through a condensing zone into a receiving chamber. It will be understood that when the catalyst flows concurrently, or countercurrently, with the reactants in a reaction chamber, the catalyst will be thereafter suitably separated from their reaction mixture by filtration, etc. The reaction mixture will be predominantly a mixture of benconditions set forth in the examples. As it will be apparent to those skilled in the art. a wide variety of other aromatic nitriles may be prepared by a suitable modification oi the alkyl aromatic hydrocarbon reactants.

A reactor consisting of a shell containing a catalyst chamber heated by circulating a heattransfer medium thereover, and containing 100 parts by weight of catalystcomprising 10 parts by weight of vanadium pentoxide supported on 90 parts by weight of alumina, was used in each of the runs. Ammonia and various alkyl aromatic hydrocarbons were introduced in the vaporphase into the reactor. passed from the reactor, through a condenser, into a first receiving chamber. Hydrogen and unchanged ammonia were collected in a second receiving chamber and then separated from each other. The nitriles and the unchanged alkyl aro-.

matic hydrocarbons remained in the first receiving chamber and were subsequently separated by distillation. The pertinent data and the results of each run are tabulated in the following" table:

Alkyl Converrsion em- .per ass Liquid Moi Ratio S ace 'Ammcnla'to Percent Nitriles am e Hydro ture 81w Hydm Weight of Formed 0. carbon in it carbon Hydro- Reactant F. y I carbon Y Charged i Toluene... 1,050 0.9 2:1 6.4 Benzonitriie. 2 Xylene. 1,000 1.0 2:1 10.0 Tolunitrile zonitrile, hydrogen, unchanged toluene, and unchanged ammonia. The benzonitrile and the unchanged toluene will be condensed in passing through the condensing zone and will b retained in the receiving chamber. Benzonitrile can be separated from the unchanged toluene by any of the numerous and well known separation procedures, such as fractional distillation. Similarly, the uncondensed hydrogen and unchanged ammonia can be separated from each other. The

unchanged toluene and ammonia can be recycled,

with or without fresh toluene and ammonia, to the process.

It will be apparent that the process may be operated as a batch or discontinuous process as by using a catalyst-bed-type reaction chamber in which the catalytic and regeneration operations alternate. With a series of such reaction chamthe catalytic operation is taking place in one or more of the reaction chambers, regeneration of the catalyst will be taking place in one or more of the other reaction chambers. correspondingly, the process may be continuous when we use one or more catalyst chambers through which the catalyst flows in contact with the reactants. In such a continuous process, the catalyst will now through the reaction zone in contact with the reactants and will thereafter be separated from the reaction mixture, as'for example, by accumulating the catalyst on a suitable filter medium, before condensing the reaction mixture. In a continuous process, therefore, the catalyst-fresh or regenerated-eand the reactantsfresh or recycle-will continuously flow through a reaction chamber.

The following detailed examples are for the purpose of illustrating modes of preparing aromatic nitriles in accordance with the process of our invention, it being clearly understood that It will be'apparent that the present invention provides an efiiclent, inexpensive and safe process for obtaining aromatic nitriles, particu-r larly those of the benzene series. Our process is of considerable value in making available-relatively inexpensive aromatic nitriles which are useful, for example, as intermediates in organic synthesis.

This application is continuation-in-part of copending application, 'Serial Number 553,291, filed September 8, 1944, now abandoned.

Although the present invention has been de? scribed in conjunction with preferred embodiments, it is to be understood that modifications and variations may be resorted to without de-" parting from the spirit and scope of the invention, .as those skilled in the art will readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims.

We claim:

1. A process for the production oijromatic nitriles. which comprises contacting an aromatic hydrocarbon having at least one nuclear hydrogen replaced by a univalent, aliphatic, non-acetylenic hydrocarbon radical, and containing 'at least seven and up to eleven, inclusive, carbon atoms per molecule, with ammonia, in gaseous phase, at temperatures falling within the range varying between about 850 F. and about 1250 F., in the presence of a catalyst comprising a vanadium oxide.

2. A process for the production of aromatic nitriles, which comprises contacting an aromatic hydrocarbon having at least one nuclear hydro-.

gen replaced by a univalent, aliphatic, nonacetylenic hydrocarbon radical, and containing at least seven and upto eleven, inclusive, carbon atoms per molecule, with ammonia. in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075' The reaction mixture was 7 F., in the presence of a vanadium oxide supported on a catalyst support.

3. A process for the production of aromatic nitriles, which comprises contacting an aromatic hydrocarbon having at least one nuclear hydrogen replaced by a univalent, aliphatic, non-acetyienic hydrocarbon radical, and containing at least seven and up to eleven, inclusive, carbon atoms per molecule, with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of vanadium pentoxide supported on alumina.

4. A process for the production of aromatic nitriles, which comprises contacting a methylsubstituted aromatic hydrocarbon containing at least seven and up to eleven, inclusive, carbon atoms per molecule, with ammonia, in gaseous phase, at temperatures falling within the range varying between about 850 F. and about 1250" F., in the presence of a catalyst comprising a vanadium oxide.

5. A process for the production of aromatic nitriles, which comprises contacting a methylsubstituted aromatic hydrocarbon containing at least seven and up to eleven, inclusive, carbon atoms per molecule, with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of a vanadium oxide supported on a catalyst support.

6. A process for the production of aromatic nitriles, which comprises contacting a methylsubstituted aromatic hydrocarbon containing at least seven and up to eleven, inclusive, carbon atoms per molecule, with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of vanadium pentoxide supported on alumina.

7. A process for the production of aromatic nitriles of the benzene series, which comprises contacting a methyl-substituted benzene with ammonia, in gaseous phase, at temperatures falling within the range varying between about 850 F. and about 1250 F,'., in the presence of a vanadium oxide.

8. A. process for the production of aromatic ni-triles of the benzene series, which comprises contacting a methyl-substituted benzene with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F'., in the presence of a vanadium oxide supported on a catalyst support.

9. A process for the production of aromatic nitriles oi the benzene series, which comprises contacting a methyl-substituted benzene with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of vanadium pentoxide supported on alumina.

10. A process for the production oi benzonitrile, which comprises contacting toluene with V ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of vanadium pentoxide supported on alumina.

11. A process for the production of aromatic nitriles oi the benzene series, which comprises contacting a xylene with ammonia, in gaseous phase, at temperatures falling within the range varying between about 925 F. and about 1075 F., in the presence of vanadium pentoxide supported on alumina.

WILLIAM I. DENTON. RICHARD B. BISHOP.

REFERENCES CITED The following references are of. record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,318,633 Weiss et a1 Oct. 14, 1919 1,920,795 Jaeger Aug. 1, 1933 1,934,838 Andrussow Nov. 14, 1933 2,331,968 Forney Oct, 19, 1943 2,381,470 Teter Aug. 7, 1945 2,381,471 Teter Aug. 7, 1945 2,381,472 Teter Aug. 7, 1945 2,381,473 Teter Aug. 7, 1945 2,381,709 Apgar et a1 Aug. 7, 1945 

